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This paper details the first dedicated production of homogeneous nanocrystalline particles of mixed actinide oxide solid solutions containing americium. The target compositions were U 0.75 Pu 0.20 Am 0.05 O 2 , U 0.90 Am 0.10 O 2 and U 0.80 Am 0.20 O 2 . After successful hydrothermal synthesis and chemical characterisation, the nanocrystals were sintered and their structure and behaviour under self-irradiation were studied by powder XRD. Cationic charge distribution of the as-prepared nanocrystalline and sintered U 0.80 Am 0.20 O 2 materials was investigated applying U M 4 and Am M 5 edge high energy resolution XANES (HR-XANES). Typical oxidation states detected for the cations are U(iv)/U(v) and Am(iii)/Am(iv). The measured crystallographic swelling was systematically smaller for the as-synthesised nanoparticles than the sintered products. For sintered pellets, the maximal volumetric swelling was about 0.8% at saturation, in line with literature data for PuO 2 , AmO 2 , (U,Pu)O 2 or (U,Am)O 2 ., Competing Interests: The authors declare no conflict of interest., (This journal is © The Royal Society of Chemistry.)

Nanograined nuclear materials are expected to have a better performance as spallation targets and nuclear fuels than conventional materials, but many basic properties of these materials are still unknown. The present work aims to contribute to their better understanding by studying the effect of grain size on the melting and solid-solid transitions of nanograined UC 2-y . We laser-heated 4 nm-10 nm grain size samples with UC 2-y as the main phase (but containing graphite and UO 2 as impurities) under inert gas to temperatures above 3000 K, and their behavior was studied by thermal radiance spectroscopy. The UC 2-y solidification point (2713(30) K) and α-UC 2 to β-UC 2 solid-solid transition temperature (2038(10) K) were observed to remain unchanged when compared to bulk crystalline materials with micrometer grain sizes. After melting, the composite grain size persisted at the nanoscale, from around 10 nm to 20 nm, pointing to an effective role of carbon in preventing the rapid diffusion of uranium and grain growth.

Thorium carbide to be tested as target material for the production of 225 Ac with the ISOL method, was produced via carbothermal reduction of ThO 2 nanoparticles by graphite and graphene oxide, respectively. The use of graphene oxide (GO) as carbon source resulted in a reduced reactivity compared to graphite, confirmed by the presence of unreacted ThO 2 mainly in the core of the samples. The reacted ThO 2 or ThC 2 -GO showed a faster reactivity in air, mainly observed as ThC 2 amorphization. The specific surface area of the ThC 2 -GO samples was almost doubled compared to ThC 2 -graphite samples. The effect of these microstructural features was analysed in terms of thermal diffusivity and calculated thermal conductivity that were both reduced in ThC 2 -GO samples, however the difference with ThC 2 -graphite samples decreased at increasing temperature. The present study shows that the use of unreduced GO inhibits the solid-state reaction between ThO 2 and C; on the other hand, the high reactivity of the ThC 2 so produced is expected to be beneficial for the 225 Ac production with the ISOL method, affording a high release efficiency. It is expected that the use of reduced GO could represent a good solution for highly efficient ThC 2 targets.

This paper presents an experimental study about the preparation, by electrospinning, of uranium carbide fibers with nanometric grain size. Viscous solutions of cellulose acetate and uranyl salts (acetate, acetylacetonate, and formate) on acetic acid and 2,4-pentanedione, adjusted to three different polymer concentrations, 10, 12.5, and 15 weight %, were used for electrospinning. Good quality precursor fibers were obtained from solutions with a 15% cellulose acetate concentration, the best ones being produced from the uranyl acetate solution. As-spun precursor fibers were then decomposed by slow heating until 823 K under argon, resulting in a mixture of nano-grained UO 2 and C fibers. A last carboreduction was then carried out under vacuum at 2073 K for 2 h. The final material displayed UC 2-y as the major phase, with grain sizes in the 4 nm-10 nm range. UO 2+x was still present in moderate concentrations (~30 vol.%). This is due to uncomplete carboreduction that can be explained by the fiber morphology, limiting the effective contact between C and UO 2 grains.

Actinide research at the nanoscale is gaining fundamental interest due to environmental and industrial issues. The knowledge of the local structure and speciation of actinide nanoparticles, which possibly exhibit specific physico-chemical properties in comparison to bulk materials, would help in a better and reliable description of their behaviour and reactivity. Herein, the synthesis and relevant characterization of PuO 2 and ThO 2 nanoparticles displayed as dispersed colloids, nanopowders, or nanostructured oxide powders allow to establish a clear relationship between the size of the nanocrystals constituting these oxides and their corresponding An(iv) local structure investigated by EXAFS spectroscopy. Particularly, the first oxygen shell of the probed An(iv) evidences an analogous behaviour for both Pu and Th oxides. This observation suggests that the often observed and controversial splitting of the Pu-O shell on the Fourier transformed EXAFS signal of the PuO 2 samples is attributed to a local structural disorder driven by a nanoparticle surface effect rather than to the presence of PuO 2+ x species., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Both AmAlO 3 and PuAlO 3 perovskites have been synthesized and characterized using powder X-ray diffraction (XRD), Raman spectroscopy, Fourier transform infrared spectroscopy (FT-IR), and 27 Al magic angle spinning nuclear magnetic resonance spectroscopy (MAS NMR). AmAlO 3 perovskite showed a rhombohedral configuration (space group R 3̅ c ) in agreement with previous studies. The effect of americium α-decay on this material has been followed by XRD and 27 Al MAS NMR analyses. In a first step, a progressive increase in the level of disorder in the crystalline phase was detected, associated with a significant crystallographic swelling of the material. In a second step, the crystalline AmAlO 3 perovskite was progressively converted into amorphous AmAlO 3 , with a total amorphization occurring after 8 months and 2 × 10 18 α-decays/g. For the first time, PuAlO 3 perovskite was synthesized with an orthorhombic configuration (space group Imma ), showing an interesting parallel to CeAlO 3 and PrAlO 3 lanthanide analogues. High-temperature XRD was performed and showed a Imma → R 3̅ c phase transition occurring between 473 and 573 K. The thermal behavior of R 3̅ c PuAlO 3 was followed from 573 to 1273 K, and extrapolation of the data suggests that cubic plutonium perovskite should become stable at around 1850 K ( R 3̅ c → Pm 3̅ m transition).

Fundamental knowledge on intrinsic plutonium colloids is important for the prediction of plutonium behaviour in the geosphere and in engineered systems. The first synthetic route to obtain salt-free intrinsic plutonium colloids by ultrasonic treatment of PuO 2 suspensions in pure water is reported. Kinetics showed that both chemical and mechanical effects of ultrasound contribute to the mechanism of Pu colloid formation. In the first stage, fragmentation of initial PuO 2 particles provides larger surface contact between cavitation bubbles and solids. Furthermore, hydrogen formed during sonochemical water splitting enables reduction of Pu(IV) to more soluble Pu(III), which then re-oxidizes yielding Pu(IV) colloid. A comparative study of nanostructured PuO 2 and Pu colloids produced by sonochemical and hydrolytic methods, has been conducted using HRTEM, Pu L III -edge XAS, and O K-edge NEXAFS/STXM. Characterization of Pu colloids revealed a correlation between the number of Pu-O and Pu-Pu contacts and the atomic surface-to-volume ratio of the PuO 2 nanoparticles. NEXAFS indicated that oxygen state in hydrolytic Pu colloid is influenced by hydrolysed Pu(IV) species to a greater extent than in sonochemical PuO 2 nanoparticles. In general, hydrolytic and sonochemical Pu colloids can be described as core-shell nanoparticles composed of quasi-stoichiometric PuO 2 cores and hydrolyzed Pu(IV) moieties at the surface shell.

Cubic fluorite-type phases have been reported in the U(IV)O2-Bi2O3 system for the entire compositional range, but an unusual non-linear variation of the lattice parameter with uranium substitution has been observed. In the current extensive investigation of the uranium(iv) oxide-bismuth(iii) oxide system, this behaviour of the lattice parameter evolution with composition has been confirmed and its origin identified. Even under inert atmosphere at 800 °C, U(IV) oxidises to U(V)/U(VI) as a function of the substitution degree. Thus, using a combination of three methods (XRD, XANES and Raman) we have identified the formation of the BiU(V)O4 and Bi2U(VI)O6 compounds, within this series. Moreover, we present here the Rietveld refinement of BiU(V)O4 at room temperature and we report the thermal expansion of both BiU(V)O4 and Bi2U(VI)O6 compounds.